Compound, resist composition for color filter, color filter, dyed  fiber, and dyeing method

ABSTRACT

An object is to provide a compound having high color developability and excellent heat resistance, and a resist composition for a color filter and a color filter that contain the dye composition. Another object is to provide a dyed polyamide fiber product having excellent wet rubbing fastness. The objects are achieved by a compound represented by the following general formula (1):

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a compound, a resist composition for acolor filter, a color filter, and a dyed fiber.

Description of the Related Art

Displays using a light emitting device such as a liquid crystal, anorganic electroluminescence (organic EL), and a light emitting diode(LED) are widely used in fields such as portable terminals typified bysmart phones and tablet terminals, television receivers and digitalsignage systems. In recent years, high definition displays withtypically 4K or 8K resolution have become widely used, so that colorfilters for use in the displays also are required to achieve improvedperformance corresponding to the high definition.

The size of picture elements is reduced in high definition displays, sothat the aperture ratio of the picture elements is lowered.Consequently, the light intensity of light emitting devices is requiredto be increased in order to obtain bright and clear color development.In order to increase the light intensity of light emitting devices, dyesexcellent in color development such as C.I. Acid Red 52 (AR52) and C.I.Acid Red 289 (AR289) are used (Japanese Patent No. 4911256 and JapanesePatent Application Laid-Open No. 2016-38463). Meanwhile, a dye withimprovement on AR289 to achieve better light resistance is disclosed(Japanese Patent Application Laid-Open No. 2016-108545).

Due to the excellent color developability, AR289 is also used in dyeingsilk scarfs and the like. Due to the poor wet rubbing fastness thereof,however, the wearability in a sweating state is restricted. Chemicalsthat enhance the bonding between a fiber and the dye have been thereforeinvestigated.

SUMMARY OF THE INVENTION

Color filters for use in smart phones or high-definition displays having4K or 8K resolution tend to be exposed to increased heat generated froma light emitting device due to the enhanced light intensity of the lightemitting device. AR289 and AR52 that are conventionally used have goodcolor developability but poor in heat resistance. A compound havingexcellent heat resistance, therefore, needs to be developed.

Also, a dye for dyeing fiber having color developability equivalent tothat of AR289, and excellent wet rubbing fastness, needs to bedeveloped.

An object of the present invention is to provide a dye compound havinghigh color developability and excellent heat resistance. Another objectof the present invention is to provide a resist composition for a colorfilter and a color filter, with use of the dye composition.

A further another object of the present invention is to provide a dyeand a dyed product having high color developability and excellent wetrubbing fastness.

The problem described above can be solved by using a compoundrepresented by the following general formula (1).

In the general formula (1), R¹ represents a straight-chain or branchedalkyl group having 5 carbon atoms, R² represents a hydrogen atom, asulfo group, a sulfonate group, a sulfonato group, or a sulfonamidegroup, and R³ and R⁴ each independently represent a sulfo group, asulfonate group, a sulfonato group, or a sulfonamide group, wherein atleast one of R² to R⁴ is a sulfonate ion. According to the presentinvention, a resist composition for a color filter having high colordevelopability and excellent heat resistance can be obtained.

Further, according to the present invention, a color filter havingexcellent color development performance and heat resistance can beobtained.

Furthermore, according to the present invention, a polyamide-containingdyed fiber having high color developability and excellent wet rubbingfastness can be obtained.

According to the present invention, a compound having high colordevelopability and excellent heat resistance can be provided. Further,according to the present invention, a resist composition for a colorfilter and a color filter having high color developability and excellentheat resistance can be provided. Furthermore, according to the presentinvention, a polyamide-containing dyed fiber having high colordevelopability and excellent wet rubbing fastness can be obtained.

Further features of the present invention will become apparent from thefollowing description of exemplary embodiments with reference to theattached drawing.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGURE is a chart illustrating thermal gravity/differential thermalanalysis (TG-DTA) data on a compound (1) of the present invention.

DESCRIPTION OF THE EMBODIMENTS

Preferred embodiments of the present invention will now be described indetail in accordance with the accompanying drawings.

The present invention is described in detail as follows, though thepresent invention is not limited thereto.

As a result of extensive study to solve the problem, the presentinventors have found that using a compound represented by the followinggeneral formula (1), high color developability and excellent heatresistance can be achieved. The present inventors have further foundthat excellent wet rubbing fastness can be also achieved.

in the general formula (1), R¹ each independently represent astraight-chain or branched alkyl group having 5 carbon atoms, R²represents a hydrogen atom, a sulfo group, a sulfonate group, asulfonato group, or a sulfonamide group, and R³ and R⁴ eachindependently represent a sulfo group, a sulfonate group, a sulfonatogroup, or a sulfonamide group, wherein at least one of R² to R⁴ is asulfonato group.

The reason why the compound represented by the general formula (1)achieves improved heat resistance is presumably that the introduction ofa sulfo group (—SO₃H), a sulfonate group, a sulfonato group (—SO₃ ⁻), ora sulfonamide group (−SO₂NR_(A)R_(B); wherein R_(A) and R_(B) eachrepresent a hydrogen atom or an alkyl group) at the 2-position or7-position of a xanthene ring forms a hydrogen bond, which enhances thestacking effect between molecules.

Compounds represented by the general formula (1) with a total number ofa sulfo group, a sulfonate group, a sulfonato group and a sulfonamidegroup of 1 as a whole have low solubility in water or organic solvents,being inclined to have lowered color developability similar to apigment. In contrast, compounds represented by the general formula (1)with a total number of a sulfonic acid group, a salt of a sulfonic acidgroup, a sulfonate ion and a sulfonamide group of 4 or more as a wholehave high water solubility and poor solubility in organic solvents,being inclined to have lowered heat resistance.

Also, with R¹ in the general formula (1) having 4 or less carbon atoms,the heat resistance is lowered due to reduction in affinity to a resin,while with R¹ having 6 or more carbon atoms, the heat resistance islowered due to enhanced thermal mobility resulting from the increasedflexibility of the R¹ molecular structure.

Examples of the alkyl group represented by R¹ in the general formula (1)include a straight-chain or branched alkyl group having 5 carbon atoms,though not particularly limited thereto. Specific examples thereofinclude an n-pentyl group, a (1-methyl)butyl group, a (2-methyl)butylgroup, a (3-methyl)butyl group, a (1-ethyl)propyl group, a(1,1-dimethyl)propyl group, a (1,2-dimethyl)propyl group and a(2,2-dimethyl)propyl group. In particular, an n-pentyl group and a(2,2-dimethyl)propyl group are more preferred due to high colordevelopability and excellent heat resistance.

The sulfonate group represented by R² to R⁴ in the general formula (1)is not particularly limited, and specific examples thereof includelithium sulfonate, sodium sulfonate and potassium sulfonate. Inparticular, sodium sulfonate is preferred due to high colordevelopability and excellent heat resistance.

The sulfonamide group represented by R² to R⁴ in the general formula (1)is not particularly limited, and specific examples thereof include asulfonamide group, an N-methylsulfonamide group, anN,N-dimethylsulfonamide group, an N-ethylsulfonamide group, anN,N-diethylsulfonamide group, an N-propylsulfonamide group, anN,N-dipropylsulfonamide group, an N-butylsulfonamide group, anN,N-dibutylsulfonamide group, an N-pentylsulfonamide group, anN,N-dipentylsulfonamide group, an N-hexylsulfonamide group, anN,N-dihexylsulfonamide group, an N-octylsulfonamide group, anN,N-dioctylsulfonamide group, an N-(2-ethylhexyl)sulfonamide group, anN,N-bis(2-ethylhexyl)sulfonamide group, an N-(1-methylhexyl)sulfonamidegroup, an N-(1-methylheptyl)sulfonamide group, anN-methyl-N-butylsulfonamide group, an N-methyl-N-pentylsulfonamidegroup, an N-methyl-N-hexylsulfonamide group, anN-methyl-N-octylsulfonamide group, an N-phenylsulfonamide group, anN-(p-methylphenyl) sulfonamide group, an N-pyrrolidylsulfonyl group andan N-piperidylsulfonyl group. In particular, an N-octylsulfonamidegroup, an N-(2-ethylhexyl)sulfonamide group and an N-piperidylsulfonylgroup are more preferred due to high color developability and excellentheat resistance.

In the general formula (1), R² to R⁴ are more preferably a sulfo group,a sulfonato group or a sulfonamide group due to having high colordevelopability and excellent heat resistance. In particular, R² and R³can be a sulfo group or a sulfonamide group, and R⁴ can be a sulfonatogroup.

The compound represented by the general formula (1) includes tautomersrepresented by general formulas (2) and (3). In addition, with R⁴ beinga sulfonic acid group, a salt of a sulfonic acid group or a sulfonateion, an isomer represented by a general formula (4) is also present. Allof the tautomers represented by the general formulas (2) to (4) areincluded in the scope of the present invention.

The R¹ to R⁴ in the general formulas (2) and (3) are the same as the R¹to R⁴ in the general formula (1). Also, the R¹ to R³ in the generalformula (4) are the same as the R¹ to R³ in the general formula (1).

A compound having the structure represented by the general formula (1)can be synthesized with reference to known methods described in JapanesePatent No. 5451556, Japanese Patent Application Laid-Open No.2016-108545, etc.

The compound represented by the general formula (1) of the presentinvention can be any compound shown in the following (1) to (56), thoughthe present invention is not limited thereto.

Among those, the compounds (1), (2), (3), (5), (7), (8), (9), (10),(11), (15), (17), (31), (33), (36), (38), (41), (44), (46) and (49) arepreferred, and, in particular, the compounds (1), (7), (9), (15), (17),(31), (33), (38), (41), (44) and (46) are more preferred due to havinghigh color developability and excellent heat resistance.

The compounds represented by the general formula (1) may be used singlyor in combinations of two or more for adjustment of color tone dependingon applications. Furthermore, the compound may be used in combinationwith a known pigment or dye. Two or more known pigments or dyes may beused in combination.

The pigments for use are not particularly limited and examples thereofinclude C.I. Pigment Red 48, C.I. Pigment Red 49, C.I. Pigment Red 52,C.I. Pigment Red 58, C.I. Pigment Red 63, C.I. Pigment Red 81, C.I.Pigment Red 122, C.I. Pigment Red 155, C.I. Pigment Red 166, C.I.Pigment Red 169, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I.Pigment Red 209, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I.Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I.Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 27 andC.I. Pigment Violet 39.

<Resist Composition for Color Filter>

A resist composition for a color filter with use of the compoundrepresented the general formula (1) is described as follows.

Due to having high color developability and excellent heat resistance,the compound represented by the general formula (1) can be suitably usedas a resist composition for a color filter. Also, with use of the resistcomposition, a color filter having high color developability andexcellent heat resistance can be obtained.

The resist composition for a color filter contains a binder resin, amedium, and the compound of the present invention as a colorant. Anaspect of the method for manufacturing the resist composition for acolor filter is described, though the present invention is not limitedthereto. For example, a compound represented by the general formula (1)and a binder resin are added to a solvent while being stirred. On thisoccasion, a polymerizable monomer, a polymerization initiator, aphotoacid generator, and the like may be added thereto on an as neededbasis. The material is then stably dissolved or finely dispersed in amedium with a mechanical shearing force applied from a disperser, sothat the resist composition for a color filter of the present inventioncan be obtained.

[Binder Resin]

The binder resin for use in the resist composition is not particularlylimited, and examples thereof include one that allows either one of thephotoirradiated part and the light-shielding part in exposure forforming picture elements to be dissolved in an organic solvent, analkaline aqueous solution, water or a commercially available developer.In particular, from the viewpoints of workability and processabilityafter manufacturing of the resist, a binder resin having a compositionthat allows development in water or an alkaline aqueous solution can beemployed.

The binder resin is not particularly limited, and examples of the resinfor use include one obtained by copolymerization of a hydrophilicpolymerizable monomer having acrylic acid, methacrylic acid,N-(2-hydroxyethyl)acrylamide, N-vinylpyrrolidone or an ammonium salt anda lipophilic polymerizable monomer such as an acrylate, a methacrylate,vinyl acetate, styrene, and N-vinylcarbazole at a proper mixing ratiousing a known method.

The binder resin may be used in combination with a radical-polymerizablemonomer having an ethylenic unsaturated group, a cationic polymerizablemonomer having an oxirane ring or an oxetane ring, a radical generator,an acid generator and a base generator.

The binder resin of this type can be used as a negative-type resistcomposition. In other words, the solubility of the material is reducedat the exposed part by exposure, so that the light-shielding part isremoved by developing.

A combination of a resin having a group that is cleaved by an acid andan acid generator that generates an acid by exposure may be also used.Examples include a resin having a quinone diazide group, apolyhydroxystyrene tert-butyl carbonate ester, and a tetra-hydropyranylether.

The binder resin of this type can be used as a positive-type resistcomposition. In other words, the solubility of the material is improvedat the exposed part by exposure, so that the exposed part is removed bydeveloping.

For the negative-type resist composition, a polymerizable monomer to beaddition polymerized by exposure (hereinafter also referred to as“photopolymerizable monomer”) can be used. The photopolymerizablemonomer is not particularly limited, and can be, for example, a compoundhaving at least one addition polymerizable ethylenic unsaturated doublebond in a molecule, with a boiling point of 100° C. or higher at normalpressure.

Specific examples include: monofunctional acrylates and monofunctionalmethacrylates such as polyethylene glycol monoacrylate, polyethyleneglycol monomethacrylate, polypropylene glycol monoacrylate,polypropylene glycol monomethacrylate, phenoxyethyl acrylate, andphenoxyethyl methacrylate; polyfunctional acrylates and polyfunctionalmethacrylates such as polyethylene glycol diacrylate, polyethyleneglycol dimethacrylate, polypropylene glycol diacrylate, polypropyleneglycol dimethacrylate, trimethylolethane triacrylate, trimethylolethanetrimethacrylate, trimethylolpropane triacrylate, trimethylolpropanetrimethacrylate, trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, neopentylglycol diacrylate, neopentylglycoldimethacrylate, pentaerythritol tetraacrylate, pentaerythritoltetramethacrylate, pentaerythritol triacrylate, pentaerythritoltrimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritolhexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritolpentamethacrylate, hexanediol diacrylate, hexanediol dimethacrylate,trimethylolpropane tri(acryloyloxy propyl)ether, tri(acryloyloxyethyl)isocyanurate, tri(acryloyloxy ethyl)cyanurate, glyceroltriacrylate, and glycerol trimethacrylate; and polyfunctional acrylatesand polyfunctional methacrylates that can be obtained by adding ethyleneoxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane and glycerol, and then acrylating or methacrylating the reactionproduct. Furthermore, urethane acrylates, polyester acrylates,polyfunctional epoxyacrylates or epoxymethacrylates as reaction productsof an epoxy resin and acrylic acid or methacrylic acid can be also used.

Among the photopolymerizable monomers, trimethylolpropane triacrylate,trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate,pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate,dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, anddipentaerythritol pentamethacrylate are preferably used. Thephotopolymerizable monomers may be used singly or in combinations of twoor more on an as needed basis.

The content of the photopolymerizable monomer is preferably 5 to 50 mass%, more preferably 10 to 40 mass %, relative to the mass of the resistcomposition (total solid content) of the present invention. With thecontent being 5 to 50 mass %, the sensitivity to exposure and thestrength of photographic paper can be further enhanced, and goodadhesion of the resist composition can be obtained.

To a resist composition of the negative type, a photopolymerizationinitiator may be added. The photopolymerization initiator is notparticularly limited, and examples thereof include a vicinalpolyketoaldonyl compound, an α-carbonyl compound, an acyloin ether,various quinone compounds, a combination of triallyl imidazole dimer andp-amino phenyl ketone, and a trioxadiazole compound. In particular,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (trade name:IRGACURE 369 manufactured by BASF Corporation) can be used. Yet, informing picture elements from the resist composition of the presentinvention by using electron beam irradiation, the photopolymerizationinitiator is not necessarily required.

To a resist composition of the positive type, a photoacid generator maybe added thereto on an as needed basis. The photoacid generator for useis not particularly limited, and examples thereof include knownphotoacid generators such as salts of an onium ion, i.e., a sulfoniumion, an iodonium ion, a selenium ion, an ammonium ion, or a phosphoniumion, and an anion.

The sulfonium ion is not particularly limited, and examples thereofinclude triphenylsulfonium, tri-p-trisulfonium, tri-o-trisulfonium,tris(4-methoxyphenyl)sulfonium, 1-naphthyl diphenylsulfonium, diphenylphenacylsulfonium, phenylmethyl benzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, dimethyl phenacylsulfonium, and phenacyltetrahydrothiophenium.

Examples of the iodonium ion include diphenyliodonium,di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium,bis(4-methoxyphenyl)iodonium, and (4-octyloxyphenyl)phenyliodonium.

The selenium ion is not particularly limited, and examples thereofinclude a triarylselenium such as triphenylselenium,tri-p-tolylselenium, tri-o-tolylselenium, tris(4-methoxyphenyl)selenium,1-naphthyldiphenylselenium, tris(4-fluorophenyl)selenium,tri-l-naphthylselenium, and tri-2-naphthylselenium.

Examples of the ammonium ion include a tetraalkylammonium such astetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium,triethylmethylammonium, tetraethylammonium, trimethyl-n-propylammonium,trimethylisopropylammonium, trimethyl-n-butylammonium, andtrimethylisobutylammonium.

The phosphonium ion is not particularly limited, and examples thereofinclude tetraphenylphosphonium, tetra-p-tolylphosphonium,tetrakis(2-methoxyphenyl)phosphonium, triphenylbenzylphosphonium,triphenylphenacylphosphonium, triphenylmethylphosphonium,triethylbenzylphosphonium, and tetraethylphosphonium.

The anion is not particularly limited, and examples thereof include: aperhalogenate ion such as ClO₄ ⁻ and BrO₄ ⁻; a halogenated sulfonate ionsuch as FSO₃ ⁻ and ClSO₃ ⁻, a sulfate ion such as CH₃SO₄ ⁻, CF₃SO₄ ⁻ andHSO₄ ⁻; a carbonate ion such as HCO₃ ⁻ and CH₃CO₃ ⁻; an aluminate ionsuch as AlCl₄ ⁻ and AlF₄ ⁻; a hexafluorobismuthate ion, a carboxylateion such as CH₃COO⁻, CF₃COO^('1), C₆H₅COO⁻, CH₃C₆H₄COO⁻, C₆F₅COO⁻ andCF₃C₆H₄COO⁻; an arylborate ion such as B (C₆H₅)₄ ⁻ andCH₃CH₂CH₂CH₂B(C₆H₅)₃ ⁻; a thiocyanate ion, and a nitrate ion, though notlimited thereto.

[Medium]

In the resist composition, water or an organic solvent may be used asthe medium for dissolving or dispersing a compound represented by thegeneral formula (1), a binder resin, and a photopolymerizable monomer, aphotopolymerization initiator and a photoacid generator that are addedon an as needed basis.

The organic solvent is not particularly limited, and examples thereofinclude cyclohexanone, ethyl cellosolve acetate, butyl cellosolveacetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether,ethylbenzene, 1,2,4-trichlorobenzene, ethylene glycol diethyl ether,xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycolmonomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methanol,ethanol, isopropanol, butanol, methyl isobutyl ketone, and a petroleumsolvent. In particular, propylene glycol monomethyl ether is suitablyused.

The organic solvents may be used singly or in combinations of two ormore.

[Colorant]

As the colorant to constitute the resist composition, the compoundrepresented by the general formula (1) is used. The compounds may beused singly or in combinations of two or more. In order to obtaindesired spectral characteristics, other known dyes and/or pigments maybe used in combination for color matching. The dyes that can be usedtogether is not particularly limited, and examples include a condensedazo compound, an azo-metal complex, a diketo pyrrolopyrrole compound, ananthraquinone compound, a quinacridone compound, a naphthol compound, abenzimidazolone compound, a thioindigo compound, a perylene compound, amethine compound, an allylamide compound, and a basic dye lake compound.The pigment that can be used together is not particularly limited, andexamples thereof include: C.I. Pigment Red 48, 49, 52, 58, 63, 81, 122,155, 166, 169, 176, 177, 209, 224, 242, 254, 255 and 264; and C.I.Pigment Violet 19, 23, 27 and 39.

The content of the dyes and/or pigments in the resist composition for acolor filter is not particularly limited as long as the total of thecontent of the compound represented by the formula (1) as the essentialcomponent of the resin composition of the present invention and thecontent of the dyes and/or pigments as the optional components is in therange of typically 0.01 to 70 parts by mass, preferably 0.5 to 50 partsby mass, more preferably 1.0 to 40 parts by mass, relative to 100 partsby mass of the total solid content of the resist composition.

To the resist composition for a color filter, an ultraviolet absorberand a silane coupling agent for enhancing the adhesion to a glasssubstrate in manufacturing a filter may be added on an as needed basisother than the additives described above.

The disperser for use in dissolving or finely dispersing the resistcomposition for a color filter is not particularly limited, and examplesthereof include a shear rotary homogenizer, a medium-type disperser suchas a ball mill, a sand mill and an attritor, and a high-pressureopposing collision-type disperser.

As described above, the resist composition for a color filter achievesthe high color developability and excellent heat resistance due tocontaining the compound represented by the general formula (1).

<Color Filter>

The color filter with use of the compound represented by the generalformula (1) is described as follows.

In a color filter having two or more picture elements with differentspectral characteristics that are adjacently disposed, the resistcomposition of the present invention is used in picture elements toconstitute at least one color of a plurality of picture element colors(e.g., red, green and blue), so that the color filter having high colordevelopability and excellent heat resistance can be obtained.

The method for forming each of the color picture elements is notparticularly limited, and examples thereof include ink jetting, printingand photolithography.

In use of ink jetting, a black matrix is formed on a glass substrate andthe resist composition for a color filter is emitted as an ink to theopening of the black matrix by using an ink jet apparatus for coloring.The resist composition is then heat-treated to form a color layer.

To the black matrix, a water repellent agent such as silicon andfluorine may be added.

In use of printing, the resist composition for a color filter is appliedand dried for the formation.

In use of photolithography, a resist composition is applied to atransparent substrate such that the dried film has a thickness of 0.1 to20 μm, preferably 0.5 to 5 μm, and dried for the formation.

Examples of the application method include bar coating, spin coating,spray coating, roll coating and slit coating.

On an as needed basis, the dried film is exposed to ultraviolet raysthrough a photo mask for the exposure. The film is then immersed in asolvent or an alkaline developer, so that uncured parts are removed forthe formation.

Alternatively, the color filter may be manufactured byelectrodeposition, transferring, etc.

The color filter can be suitably used for liquid crystal displayapparatuses, organic EL displays, organic EL devices, solid imagingdevices (CCD and CMOS), etc.

The display apparatuses may be ones that display fixed information orones that display variable information such as tachometers and speedmeters.

The liquid display apparatus is not particularly limited, and can have astructure including, for example, a backlight, a polarized film, adisplay electrode, an orientation film, a common electrode, and a colorfilter of the present invention, and a polarized film laminated insequence.

The organic EL display is not particularly limited, and can have a colorfilter of the present invention on any one of the upper and lower sidesof the multi-layer organic light emitting device.

The solid imaging device is not particularly limited, and can have astructure including, for example, a color filter of the presentinvention and a micro lens laminated on a silicon wafer having atransfer electrode and a photodiode.

<Polyamide-Containing Dyed Fiber>

A dyed product with use of the compound represented by the generalformula (1) is described as follows.

The polyamide-containing dyed fiber of the present invention is a threador fabric that contains polyamide fibers dyed with the compoundrepresented by the general formula (1). The polyamide-containing fiberis not particularly limited, and in particular, silk is preferred.

In the dye industry, dyeing by immersing threads or fabrics in a bath inwhich a dye is dissolved or dispersed (dip dyeing) is referred to asdyeing, and a method for forming a printed pattern by imparting a dye toa part of a fabric and putting another color dye on the other part isreferred to as printing, in some cases. The product dyed by any one ofthe methods is included in the dyed product of the present invention.

In dyeing, the compound represented by the general formula (1) can becontacted with a polyamide-containing fiber by any method, which may bean appropriate conventional method in the technical field. Examples ofthe dip dyeing include winch dyeing and jigger dyeing, and examples ofthe printing include screen printing, roller printing, ink jetting andelectrophotography.

EXAMPLES

With reference to Examples and Comparative Examples, the presentinvention is further described in detail as follows, though the presentinvention is not limited to the Examples. In the description, “parts”and represent “parts by mass” and “mass %”, respectively, unlessotherwise noted. The obtained compounds were identified using a ¹Hnuclear magnetic resonance spectroscopic (¹H-NMR) apparatus (ECA-400,manufactured by JEOL Ltd.) and an LC/TOF MS apparatus (LC/MSD TOF,manufactured by Agilent Technologies).

Example 1

<Manufacturing of Compound (1)>

Under nitrogen atmosphere,N-(3-amino-2,4,6-trimethylphenyl)-3,3-dimethylbutanamide (38 g, 0.153mol) was added to an N-methyl-pyrrolidone solution (100 mL) of rawmaterial A (15 g, 0.037 mol) having the following structure to cause areaction at 150° C. for 6 hours. After completion of the reaction, theproduct was cooled to room temperature, to which 100 mL of 2 mol/L ofhydrochloric acid was slowly added and stirred for 30 minutes. Afterfiltration, the product was washed with 100 mL of water, and theobtained solid was dried. The dried solid was added to 30 g of fumingsulfuric acid ice-cooled at 5° C. or lower, and stirred at 30 to 32° C.for 24 hours. After completion of the reaction, the reaction liquid wasslowly added onto 200 g of ice and stirred. After filtration, theproduct was washed with cold water, and the solid was suspended in 50 mLof water. A sodium hydroxide aqueous solution was used to adjust the pHat 7 to 8, and then acetone was used for crystallization to obtain 17.1g of the compound (1). The maximum absorption wavelength was 534 nm(H₂O).

Examples 2 to 10, and Comparative Examples 1 to 5

Each of the compounds and comparative compounds described in Table 1 wasobtained by manufacturing in the same manner as in Example 1, exceptthat N-(3-amino-2,4,6-trimethylphenyl)-2,2-dimethylpropanamide inExample 1 was replaced with an amide corresponding to the structure ofthe intended compound.

Example 11

To 5 mL of methanol solution of 15 g of the compound (1), 30 mL ofconcentrated hydrochloric acid was added and stirred for 1 hour toprecipitate a solid, which was then filtered and washed with 500 mL ofwater to obtain 10.5 g of a compound (17).

Example 12

By the same procedure as in Example 11 except that a compound (15) wasused instead of the compound (1) in Example 11, 11.2 g of a compound(31) was obtained.

Example 13

A solution of a compound (17) (5 g, 5 parts) in 50 ml of tetrahydrofuranand 2.5 parts of N,N-dimethylformaldehyde was ice-cooled, to which 11parts of thionyl chloride was slowly dropped to maintain the temperatureat 10° C. or lower. After the reaction at room temperature for 2 hours,the reaction system was ice-cooled again, and 10 parts of n-octylaminewas dropped thereto to cause a reaction at room temperature for 5 hours.After completion of the reaction, the reaction system was concentratedunder reduced pressure by an evaporator, and to which 50 mL of methanolwas added. The methanol solution was added to 50 parts of 25% aceticacid aqueous solution, and the precipitated solid was filtered. Theobtained solid was refined by column chromatography to obtain a compound(33) (2.1 g).

Examples 14 to 21

By the same procedure as in Example 13, except that the amount ofthionyl chloride (5.05 parts, in the case of one amide) was changed, andoctylamine was replaced with an amine corresponding to the structure ofthe intended compound, with the amount changed, compounds (34), (35),(36), (37), (38), (41), (44) and (46) were obtained.

[Evaluation on Heat Resistance]

The heat resistance of each of the compounds and comparative compoundswas evaluated by using a simultaneous thermal gravity/differentialthermal analyzer (TG-DTA) (trade name: STA7200RV, manufactured byHitachi High-Tech Science Corporation). In the evaluation on the heatresistance, 5 mg of a sample was heated from a temperature of 45° C. to550° C. at a temperature elevation rate of 10° C./min. FIGURE is a graphillustrating the specific weight decrease of the compound (1)manufactured in Example 1 in the thermal gravity/differential thermalanalysis (TG-DTA).

The results are shown in Table 1.

The evaluation criteria are as follows.

A: The weight decrease at 450° C. is less than 20%.

B: The weight decrease at 450° C. is 20% or more and less than 50%.

C: The weight decrease at 450° C. is 50% or more.

TABLE 1 Maximum absorption Evaluation wavelength on heat Compound (nm)resistance Example 1 Compound (1) 534 A Example 2 Compound (2) 533 AExample 3 Compound (3) 533 A Example 4 Compound (5) 532 B Example 5Compound (7) 533 A Example 6 Compound (8) 533 B Example 7 Compound (9)528 A Example 8 Compound (10) 528 A Example 9 Compound (11) 526 AExample 10 Compound (15) 528 A Example 11 Compound (17) 528 A Example 12Compound (31) 528 A Example 13 Compound (33) 528 A Example 14 Compound(34) 528 A Example 15 Compound (35) 528 A Example 16 Compound (36) 528 AExample 17 Compound (37) 528 A Example 18 Compound (38) 528 A Example 19Compound (41) 527 B Example 20 Compound (44) 528 B Example 21 Compound(46) 528 A Comparative Comparative 527 C Example 1 compound (1)Comparative Comparative 566 C Example 2 compound (2) ComparativeComparative 532 C Example 3 compound (3) Comparative Comparative 534 CExample 4 compound (4) Comparative Comparative 530 C Example 5 compound(5)

<Manufacturing of Resist Composition for Color Filter and Color Filter>

A resist composition for a color filter and a color filter weremanufactured by the following methods.

Example 22

Into 12 parts of the compound (1) synthesized in Example 1, 120 parts ofcyclohexanone was mixed and dispersed for 1 hour using an attritor(manufactured by Mitsui Mining Co., Ltd.), so that an ink (1) for resistcomposition was obtained.

Subsequently, to 96 parts of a cyclohexanone solution of 6.7 parts ofacrylic copolymer composition (weight average molecular weight Mw:10,000) with a monomer ratio of 40 mass % of n-butylmethacrylate, 30mass % of acrylic acid, and 30 mass % of hydroxyethylmethacrylate, 1.3parts of dipentaerythritol pentaacrylate, and 0.4 parts of2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone(photopolymerization initiator), 22 parts of the ink (1) for resistcomposition was slowly added and stirred at room temperature for 3hours. The reaction product was filtered with a 1.5-μm filter, so thatthe resist composition (1) for a color filter was obtained.

The resist composition (1) for a color filter applied to a glasssubstrate by spin coating was dried at 90° C. for 3 minutes, and thensubjected to whole surface exposure and post curing at 180° C., so thatthe color filter (1) was manufactured.

Examples 23 to 42

Resist compositions (2) to (21) for a color filter were obtained in thesame manner as in Example 22, except that the compound (1) in Example 22was changed to each of the compounds shown in Table 2. Color filters (2)to (21) were also manufactured by the same procedure as in Example 22,except that each of the obtained resist compositions (2) to (21) for acolor filter was used instead of the resist composition (1) for a colorfilter.

Comparative Examples 6 to 10

Resist compositions (1) to (5) for comparative color filters wereobtained in the same manner as in Example 22, except that the compound(1) in Example 22 was changed to each of comparative compounds (1) to(5). Comparative color filters (1) to (5) were also manufactured by thesame procedure as in Example 22, except that the obtained resincompositions (1) to (5) for comparative color filters were used insteadof the resist composition (1) for a color filter.

Evaluation on Heat Resistance

Each of the obtained color filters and comparative color filters wereheat-treated at 230° C. for 180 minutes and the spectral transmittancebefore and after the treatment was measured. Using a reflectiondensitometer SpectroLino (trade name, manufactured by Gretag MacbethInc.), the color difference between before and after the heat treatment(ΔE) was calculated based on the following expression in the CIE 1976L*a*b* color space (CIELAB color space) for the evaluation on heatresistance. The results are shown in Table 2.

ΔE=√{square root over ((L ₂ *−L ₁*)²+(a ₂ *−a ₁*)²+(b ₂ *−b ₁*)²)}

In the expression, the chromaticity values before the heat treatmentwere a₁*, b₁* and L₁*, and the chromaticity values after the heattreatment were a₂*, b₂* and L₂*.

The evaluation criteria are as follows.

A: ΔE is less than 3.0.

B: ΔE is 3.0 or more and less than 5.0.

C: ΔE is 5.0 or more.

TABLE 2 Evaluation on heat Compound Name ΔE resistance Example 22Compound (1) Color filter (1) 2.1 A Example 23 Compound (2) Color filter(2) 2.3 A Example 24 Compound (3) Color filter (3) 2.5 A Example 25Compound (5) Color filter (4) 3.2 B Example 26 Compound (7) Color filter(5) 2.8 A Example 27 Compound (8) Color filter (6) 3.6 B Example 28Compound (9) Color filter (7) 2.2 A Example 29 Compound (10) Colorfilter (8) 2.7 A Example 30 Compound (11) Color filter (9) 2.2 A Example31 Compound (15) Color filter (10) 2.6 A Example 32 Compound (17) Colorfilter (11) 2.1 A Example 33 Compound (31) Color filter (12) 2.2 AExample 34 Compound (33) Color filter (13) 2.5 A Example 35 Compound(34) Color filter (14) 2.3 A Example 36 Compound (35) Color filter (15)2.2 A Example 37 Compound (36) Color filter (16) 2.1 A Example 38Compound (37) Color filter (17) 2.5 A Example 39 Compound (38) Colorfilter (18) 2.8 A Example 40 Compound (41) Color filter (19) 2.6 AExample 41 Compound (44) Color filter (20) 2.4 A Example 42 Compound(46) Color filter (21) 2.5 A Comparative Comparative Comparative color5.2 C Example 6 compound (1) filter (1) Comparative ComparativeComparative color — Unevaluable Example 7 compound (2) filter (2)Comparative Comparative Comparative color 5.6 C Example 8 compound (3)filter (3) Comparative Comparative Comparative color 5.7 C Example 9compound (4) filter (4) Comparative Comparative Comparative color —Unevaluable Example 10 compound (5) filter (5)

Regarding the color developability of the compounds of the presentinvention and the comparative compounds (1) to (5), any of the compoundsexhibited high color developability. However, the comparative compound(2), i.e., C.I. Acid Red 52, and the comparative compound (5) were notable to be dissolved in a resist solvent due to too high watersolubility, so that no color filter was manufactured.

Examples 43 to 50

Resist compositions (22) to (29) for a color filter were obtained in thesame manner as in Example 22, except that 12 parts of the compound (1)in Example 22 was changed to 12 parts of the compounds and pigments atthe ratios shown in Table 3, respectively. Color filters (22) to (29)were also manufactured by the same procedure as in Example 22, exceptthat the obtained resin compositions (22) to (29) for a color filterwere used instead of the resist composition (1) for a color filter. Inthe pigments shown in Table 3, PR represents Pigment Red.

Comparative Examples 11 to 15

Resist compositions (6) to (10) for comparative color filters wereobtained in the same manner as in Example 22, except that 12 parts ofthe compound (1) in Example 22 was changed to the comparative compoundsand pigments shown in Table 2, respectively. Comparative color filters(6) to (10) were also manufactured by the same procedure as in Example22, except that the obtained resin compositions (6) to (10) forcomparative color filters were used instead of the resist composition(1) for a color filter.

[Evaluation on Heat Resistance]

Each of the obtained color filters and comparative color filters wereheat-treated at 230° C. for 300 minutes and the spectral transmittancebefore and after the treatment was measured. Using a reflectiondensitometer SpectroLino (trade name, manufactured by Gretag MacbethInc.), the color difference between before and after the heat treatment(ΔE) was calculated based on the following expression in the CIE 1976L*a*b* color space (CIELAB color space) for the evaluation on heatresistance. The results are shown in Table 3.

ΔE=√{square root over ((L ₂ *−L ₁*)²+(a ₂ *−a ₁*)²+(b ₂ *−b ₁*)²)}

In the expression, the chromaticity values before the heat treatmentwere a₁*, b₁* and L₁*, and the chromaticity values after the heattreatment were a₂*, b₂* and L₂*.

The evaluation criteria are as follows.

A: ΔE is less than 1.7.

B: ΔE is 1.7 or more and less than 2.0.

C: ΔE is 2.0 or more.

TABLE 3 Evaluation Mass on heat Compound/Pigment ratio Name ΔEresistance Example 43 Compound (17)/Pigment Blue 15:6 2/8 Color filter(22) 1.7 B Example 44 Compound (31)/Pigment Red 254 1/9 Color filter(23) 1.5 A Example 45 Compound (33)/Pigment Blue 15:6 1/9 Color filter(24) 1.6 A Example 46 Compound (34)/Pigment Blue 15:6 1/9 Color filter(25) 1.4 A Example 47 Compound (35)/Pigment Green 58 3/7 Color filter(26) 1.7 B Example 48 Compound (36)/Pigment Red 254 1/9 Color filter(27) 1.4 A Example 49 Compound (37)/Pigment Red 254 1/9 Color filter(28) 1.5 A Example 50 Compound (38)/Pigment Blue 15:6 2/8 Color filter(29) 1.9 B Comparative Comparative compound (1)/ 2/8 Comparative color3.6 C Example 11 Pigment Blue 15:6 filter (6) Comparative Comparativecompound (2)/ 1/9 Comparative color 3.5 C Example 12 Pigment Red 254filter (7) Comparative Comparative compound (3)/ 3/7 Comparative color3.5 C Example 13 Pigment Green 58 filter (8) Comparative Comparativecompound (4)/ 2/8 Comparative color 3.4 C Example 14 Pigment Blue 15:6filter (9) Comparative Comparative compound (5)/ 2/8 Comparative color3.2 C Example 15 Pigment Blue 15:6 filter (10)

As shown in Tables 2 and 3, the color filters manufactured with use ofthe compound of the present invention is superior in both of the colordevelopability and the heat resistance to the comparative color filters.

Example 51

The following printing paste was applied to a silk satin (silk: 100%),dried and then subjected to steam treatment with saturated vapor at 105°C. for 30 minutes. The fabric after the steam treatment was washed withwater, then with hot water at 60° C. containing 0.1% of a nonionicsurfactant (NEW SOAPER BS-50, manufactured by Nissin Kagaku KenkyushoCo., Ltd.) for 10 minutes, and dried after washing with water to obtainthe fabric dyed with the compound (1).

Printing Paste

Sodium alginate: 4 parts

Ammonium sulfate: 3 parts

Compound (1): 2 parts

Water: 91 parts

Examples 52 and 53, and Comparative Example 16

Instead of the compound (1) in Example 51, the compounds described inTable 4 were used to obtain the fabrics in Examples 52 and 53, andComparative Examples 16.

[Evaluation on Wet Rubbing Fastness]

Each of the fabric specimens obtained as described above was subjectedto the wet rubbing test prescribed in JIS L0849 using a type II(Gakushin type) tester, and evaluated using a staining grey scale. Basedon the staining grey scale, the specimens are classified into grades: afirst grade (severely stained) to a fifth grade (slightly stained). Theevaluation criteria in the present test are as follows.

A: Fourth grade or higher.

B: Third grade.

C: Second grade or lower.

TABLE 4 Compound Wet rubbing test results Example 51 Compound (1) Thirdto fourth grade Example 52 Compound (31) Fourth grade Example 53Compound (33) Fourth grade Comparative Comparative First to second gradeExample 11 compound (1)

It was clearly shown from the results that the dyed products with use ofthe compounds of the present invention are superior in the wet rubbingfastness to the dyed products with use of the comparative compounds.

INDUSTRIAL APPLICABILITY

The compound of the present invention has high color developability andexcellent heat resistance. The compound of the present invention can besuitably used in a resist composition for a color filter, a colorfilter, a liquid display apparatus, an organic electroluminescencedisplay apparatus, a solid imaging device, an LED device, an LEDdisplay, etc. The compound of the present invention also has excellentwet rubbing fastness, so that a dyed polyamide product with high wetrubbing fastness can be obtained.

While the present invention has been described with reference toexemplary embodiments, it is to be understood that the invention is notlimited to the disclosed exemplary embodiments. The scope of thefollowing claims is to be accorded the broadest interpretation so as toencompass all such modifications and equivalent structures andfunctions.

This application claims the benefit of Japanese Patent Application No.2017-016181, filed Jan. 31, 2017 which is hereby incorporated byreference herein in its entirety.

What is claimed is:
 1. A compound represented by the following generalformula (1):

wherein R¹ each independently represent a straight-chain or branchedalkyl group having 5 carbon atoms, R² represents a hydrogen atom, asulfo group, a sulfonate group, a sulfonato group, or a sulfonamidegroup, and R³ and R⁴ each independently represent a sulfo group, asulfonate group, a sulfonato group, or a sulfonamide group, wherein atleast one of R² to R⁴ is a sulfonato group.
 2. The compound according toclaim 1, wherein R², R³ and R⁴ each independently represent a sulfogroup, a sulfonato group, or a sulfonamide group.
 3. The compoundaccording to claim 2, wherein R² and R³ each independently represent asulfo group or a sulfonamide group, and R⁴ represents a sulfonato group.4. A resist composition for a color filter comprising the compoundrepresented by the following general formula (1):

wherein R¹ each independently represent a straight-chain or branchedalkyl group having 5 carbon atoms, R² represents a hydrogen atom, asulfo group, a sulfonate group, a sulfonato group, or a sulfonamidegroup, and R³ and R⁴ each independently represent a sulfo group, asulfonate group, a sulfonato group, or a sulfonamide group, wherein atleast one of R² to R⁴ is a sulfonato group.
 5. A color filter comprisingthe compound represented by the following general formula (1):

wherein R¹ each independently represent a straight-chain or branchedalkyl group having 5 carbon atoms, R² represents a hydrogen atom, asulfo group, a sulfonate group, a sulfonato group, or a sulfonamidegroup, and R³ and R⁴ each independently represent a sulfo group, asulfonate group, a sulfonato group, or a sulfonamide group, wherein atleast one of R² to R⁴ is a sulfonato group.
 6. A polyamide-containingdyed fiber dyed with the compound represented by the following generalformula (1):

wherein R¹ each independently represent a straight-chain or branchedalkyl group having 5 carbon atoms, R² represents a hydrogen atom, asulfo group, a sulfonate group, a sulfonato group, or a sulfonamidegroup, and R³ and R⁴ each independently represent a sulfo group, asulfonate group, a sulfonato group, or a sulfonamide group, wherein atleast one of R² to R⁴ is a sulfonato group.
 7. A method for dyeing apolyamide-containing fiber comprising contacting the compoundrepresented by the following general formula (1) with thepolyamide-containing fiber.

wherein R¹ each independently represent a straight-chain or branchedalkyl group having 5 carbon atoms, R² represents a hydrogen atom, asulfo group, a sulfonate group, a sulfonato group, or a sulfonamidegroup, and R³ and R⁴ each independently represent a sulfo group, asulfonate group, a sulfonato group, or a sulfonamide group, wherein atleast one of R² to R⁴ is a sulfonato group.